An efficient organocatalytic enantioselective cross-aldol reaction of aryl ketones with heteroaromatic trifluoromethyl ketone hydrates via enolate intermediates has been developed. The cross-aldol reactions catalyzed by Takemoto-type thiourea catalysts proceeded well under mild conditions, furnishing a variety of enantioenriched α-trifluoromethyl tertiary alcohols bearing N-heteroaromatics with good to high yields and enantioselectivities. This protocol features broad substrate scope, good functional group tolerance, and easy gram-scale preparation.